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Title: Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer

Abstract

The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. ORNL
Publication Date:
Research Org.:
Center for Nanophase Materials Sciences; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1050903
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 45; Journal Issue: 16; Journal ID: ISSN 0024-9297
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; CHAINS; COATINGS; CONFINEMENT; COPOLYMERS; DEPOSITION; ELLIPSOMETRY; FUNCTIONALS; METHACRYLATES; MONOMERS; NEUTRONS; POLYMERS; SEGREGATION; SPECTROSCOPY; SPIN; THICKNESS; THIN FILMS

Citation Formats

Lokitz, Bradley S, Wei, Jifeng, Hinestrosa Salazar, Juan P, Ivanov, Ilia N, Browning, James B, Ankner, John Francis, Kilbey, II, S Michael, and Messman, Jamie M. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer. United States: N. p., 2012. Web. doi:10.1021/ma300991p.
Lokitz, Bradley S, Wei, Jifeng, Hinestrosa Salazar, Juan P, Ivanov, Ilia N, Browning, James B, Ankner, John Francis, Kilbey, II, S Michael, & Messman, Jamie M. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer. United States. https://doi.org/10.1021/ma300991p
Lokitz, Bradley S, Wei, Jifeng, Hinestrosa Salazar, Juan P, Ivanov, Ilia N, Browning, James B, Ankner, John Francis, Kilbey, II, S Michael, and Messman, Jamie M. Sun . "Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer". United States. https://doi.org/10.1021/ma300991p.
@article{osti_1050903,
title = {Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer},
author = {Lokitz, Bradley S and Wei, Jifeng and Hinestrosa Salazar, Juan P and Ivanov, Ilia N and Browning, James B and Ankner, John Francis and Kilbey, II, S Michael and Messman, Jamie M},
abstractNote = {The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.},
doi = {10.1021/ma300991p},
url = {https://www.osti.gov/biblio/1050903}, journal = {Macromolecules},
issn = {0024-9297},
number = 16,
volume = 45,
place = {United States},
year = {2012},
month = {1}
}